DE1962588C3 - Process for the preparation of linear aromatic polyimides soluble in phenolic solvents - Google Patents

Description

and an aromatic diamine of the general formula

H ₂ NR-NH ₂

is used, with at least 30% of the remainder R

mean and X - C
Il CH ₃ Il
O p
I. or CH ₃ < represents X '-CF I ₂ - - C
Il CH ₃ Il
O —C—
ι or I.
CH ₃

-s— - so, -

- SO ₂ - Polyamic acids are known as synthetic resins for the formation of coating layers with high heat resistance, which are formed by an addition reaction of an aromatic tetracarboxylic acid dianhydride and an aromatic diamine in an aprotic organic polar solvent at a temperature below 50 ° C, preferably below 20 ° C . By applying such a polyamic acid in solution to an object such as an electrical conductor and

ίο heating the same will evaporate the solvent, and at the same time water is split off. A polyimide is obtained by condensation, so that one Coating layer with high heat resistance is obtained.

The advantages of polyamic acids stand as disadvantages of the extraordinary instability and the progressive conversion into insoluble polyimides at room temperature as opposed to what the gelling of the Solutions conditional. Therefore, one must keep such polyamic acids under refrigeration and as a solvent provide an expensive aprotic organic polar solvent. As a result, paint coatings are off such polyamic acids are very expensive.

In addition, this reaction only leads to polymers with a high degree of polymerization if the aromatic diamine is first dissolved in the polar solvent and then the aromatic tiracarboxylic acid dianhydride is gradually added to the solution. If the sequence of the additions vice versa selected or if the aromatic Tetraca ^r bonsäuredianhydrid is added as a solution, a polymer with low degree of polymerization, whereby the adjustment of the reaction conditions is complicated forms. (Literature: J. Polymer Sci. 1 [10], 1963, pp. 3135-3150 and J. App. Polymer Sci, 11. 1967. S.

609-727).

If, in addition, in the context of this known reaction scheme, instead of the tetracarboxylic acid dianhydride a tetracarboxylic acid? is used, the reaction does not start. That's why you have to Teiracarboxylic acid dianhydride before initiating the reaction heat a long period of time and dry what means a further complication in the context of this procedure.

U.S. Patents 2,710,853, 2,731,447 and 29 00 369 each describe a method according to which a heat reaction between an aromatic tetracarboxylic acid and an aliphatic diamine to form polyimides. This well-known aliphatic However, polyimides are insufficiently heat-resistant and also have very low solubility in organic solvents, so that these polyimides cannot be used as components of paints.

There is also a proposed method for production a curable, liquid coating composition, after which benzophenone tetracarboxylic dianhydride and a diamine from the group of diamines of the general formula

means,

Y is a lower alkyl or alkoxy radical, a halogen, a COOH, OH or SO ₃ H-ReSt and Z is a lower alkyl radical and that the reaction is carried out in a period of time ₍ sufficient for the imide ring closure reaction.

^ NH ₂

(with R as a divalent group from the group of C ₁ -QrAIkenes, —C— —O -

Il

—S groups
O

are heated in a phenolic solvent at a temperature below 160 ⁰ C (advertised Japanese patent application 44-9576). However, the compositions obtained by this process are polyamic acids. The polyimides obtained by splitting off water are insoluble. When benzophenonetetracarboxylic acid is used as a starting material, the reaction is difficult to carry out, so that a reaction step for completely dehydrating to form the dianhydride is required before the actual reaction, which brings about a problem.

The US-PS 32 88 754 describes a Polycuiid-PoIyimid which is modified by an organosilicon compound. The amide residues should be present to a predominant extent. The reaction is carried out at a comparatively low temperature below 70 ^° C., where imide formation is only imperfect. The modified polyamide-polyimides obtained by this known process have a comparatively low heat resistance. Although the solubility in an organic solvent increases as the proportion of the non-imide-like components increases, so that it can be operated in solution, the heat resistance and other characteristics deteriorate.

The BE-PS 6 55 654 describes in Examples 3 and 1 (pp. 19 and 20) the production of a polyimide solution by reaction of 2,4-diaminoisopropylbenzoI with 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in N, N'-dimethylformamide as solvent; the resulting polyamic acid solution becomes acetic anhydride admitted. From this Belgian patent it is not inferred that for the formation of an imide ring a Reaction at elevated temperature in a phenolic solvent is possible. The solvents used N, W "-dimethylformamide, K N'-dimeihylacetamide or N-methylpyrrolidone are very expensive substances, like that that an economic application is hardly possible. The solvent is largely lost, so that the The costs of such a procedure are extraordinarily high.

USPS 3190 856 relates to the manufacture of Polyamides. It is surprising that the starting materials according to the invention can also be used for this purpose not.

The US PS 32 77 043 describes the production of soluble in phenolic solvents polyamides. These polyamide solutions are intended for the production of coating layers, after which they have been applied the polyamide solutions by evaporation of the solvent and in particular by heating a Conversion into polyimides takes place. The polyimide is formed in situ within the adhesive layer. This is required because, according to the prior art, polyimides are insoluble in organic solvents.

The object of the invention is to provide a method that is safe under simple conditions can be carried out. The linear aromatic polyimides obtained according to the invention

should be soluble in phenolic solvents and stable in solution. In addition, as part of the Process according to the invention complete elimination of water from the aromatic tetracarboxylic acid component not necessary prior to the formation of the polyimides.

The invention is therefore a method for Preparation of linear aromatic polyimides soluble in phenolic solvents by reaction equimolar amounts of at least one aromatic tetracarboxylic acid, its anhydride or lower alkyl ester and at least one aromatic diamine in a solvent based on phenols and Heating the resulting solution to a temperature above the boiling point of water, which thereby is characterized in that at least? i0% of the tetracarboxylic acid a framework of the formula

and an aromatic diamine of the general formula

H ₂ NR-NH ₂
is used, with at least 30% of the remainder R

or

45 mean and X pit —O - CH ₃ 50 I.
—C— or
I. —C-
H CH ₃ Il
O represents 55 X '- CH ₂ - - S. CH ₃ I.
—C— or
I. Il 60 I.
CH ₃ Il
O means,

S — SO2

- -SO ₂ -

Y is a lower alkyl or alkoxy radical, a halogen, a COÖH-, OH- or SO ₃ H-ReSt and Z is a lower alkyl radical and that the reaction is carried out in a period of time ₍ sufficient for the imide ring closure reaction.

Examples of solvents based on Phenols that are used in the context of the invention are phenol, o-, in- and p-cresol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-xylenol, as well as halogenated «: derivatives, such as mono-, di-, tri-, tetra- and penta-halophenols, Mono-, di-, tri- and tetra-halo-resoles, mono-, di- and trihaloxylenol. Halogen atoms can be Cl, Br and J.

If you prefer halogenated derivatives that are liquid at room temperature, you can too Use compounds that are in a solid state at room temperature by placing them in dissolves small amounts of aromatic hydrocarbons such as toluene and xylene and the same in solution applies.

However, since the solvent is usually evaporated, and a halogenated phenol in general Phenol is teufer than an unhaogenieries, is the Use of non-halogenated phenols such as phenol, cresol or xylenol is preferable.

If a phenolic solvent is used, up to 20 or 30% of a non-solvent can be used Using solvent naphtha, toluene or xylene as a diluent following the reaction admit.

A linear aromatic polyimide is according to the invention in a clear solution with heating to a Temperature between 100 and 240 ° C produced.

It has been found that an aromatic polyimide having a fairly high molecular weight is obtained,

10

15th

20th

25th

when the molar ratio of the tracarboxylic acid and the diamines within the mixture is preferably the Has a value of 1 within a range between 0.9 and 1.1.

The properties of a linear aromatic polyimide obtained by the above reaction depend on the type of solvent and the starting materials, as well as the respective mixing ratios.

If a phenol is used as a solvent for the reaction mixture and a diamine of the general formula

Y Y

NH ₂

is used in amounts between 30 and 60 mol%, based on the total amount of aromatic diamines and at the same time the amount of Benzophenonieiracarbonsäure between 30 and 55 MoI- ⁰ Zo of the total amount of aromatic tetracarboxylic acid, one obtains an opaque polyimide solution. However, this difficulty can be remedied by increasing the proportion of benzophenone / elracarboxylic acids within the proportion of aromatic tetracarboxylic acid or by additionally using a different diamine among the three aromatic diamines mentioned

The reaction takes place in two stages, namely elimination of water and condensation in the following Reject:

HOOC COOH + H ₂ NR-NH ₂

NHOC COHN

-H ₂ O

HOOC COOH

H ₂ O

> L —NHUC — R — CÜHN — R — 1 "

Il c

- N R N — R—

Since the reaction product obtained is a polyimide, a difference occurs when this solution is used for known products with polyamic acids there is no formation of water that would lead to foaming or to Bubble formation when stoving a lacquer coating leads.

A small amount of a catalyst such as a lower alkyl tetraalkyl titanate e.g. B. tetrabutyl titanium or tetrapropyl titanate, has been found to be used as an additive during or after completion of the reaction for Evaporation of the solvent when the paint is stoved has proven advantageous. So you can received a stoved lacquer coating with a very good surface.

According to the invention, since the reaction is carried out at a high temperature, a tetracarboxylic acid be used by yourself; so it is not a step in the process for drying the reactants required before the actual reaction.

Examples of aromatic tetracarboxylic acids as components within the scope of the invention Procedure are:

S.S '^ / i'-Benzophenonetetracarboxylic acid,
Pyromellitic acid,
S ^ '^^' - Diphenyltetracarboxylic acid,
2,2 \ 3r3'-diphenyltetracarboxylic acid,
23,6,7-naphthalenetetracarboxylic acid,
Bis (3,4-dicarboxyphenyl) ether,
Bis (3,4-dicarboxyphenyl) sulfide,
Bis (3.4-dicarboxyphenyl) sulfone,
Bis (3,4-dicarboxyphenyl) methane,
Bis (3,4-dicarboxyphenyl) propane and their
Anhydrides as well as lower
Alkyl esters such as methyl esters and
Ethyl ester, these tetracarboxylic acids.
Examples of aromatic diamines according to the three general formulas mentioned are:

S ^ '- dimethyl-'M'-diaminodiphenylmethane,

S ^ '- DiethyM / i -'- diaminodiphenylmelhan,

33'-dimethoxy-4,4'-diaminodiphenylmethane,

S ^ '- diethoxy ^^' - diaminodiphenylmethane,

S ^ '- dichloro-'M'-diaminodiphenylmethane,

33'-dibromo-4,4'-diaminodiphenylmethane,

33'-dicarboxy-4,4'-diaminodiphenyimethane,

3,3'-DihydiOxy-4,4'-diaminodiphynylmcthan,

SJ'-Disulfo-'M'-diaminodiphenylmethane, ll

Diaminfestes of the formula

3,3'-Diethyl-4,4'-diaminodiphenyläthei ·, S.S'-dimelhoxy-'W-dianiinodiphenyl ether,

yp
3,: i - dichloro-4,4'-diaiTiinodipheriyIäther, 3,3'-dibromo-4,4'-diaminodiphenylether, idil

correspond and at the same time 50% or less of the remainder under the forms

3,3'-dihydroxy-4,4'-diaminodipheny lather, ι ο

SJ'Disulfo ^ '- diaminodiphenyl ether.

SJ'-Dimethyl ^ '- diaminodiphenylsilfid, 3,3'-diethyl-4,4'diaminodiphenyl sulfide, 3,3'-dimoxy-4.4'-diaminodiphenyl sulfide, 3,3 Diäihoxy-4,4'-diaminodiphenyl sulfide, S ^ '- dichloro ^ / T-diaminodipnenyl sulfide.

3.3'Dibromo-4,4'-diaminodiphenyl sulfide, SJ'-dicarboxy ^ / l'-diaminodiphenyl sulfide.

3,3'-dihydroxy-4,4'-diaminodiphenyl sulfide, 3.3'-disulfo-4,4'-diaminodiphenyl sulfide, 3.3'-dimethyl-4.4'-diaminodiphenyl sulfone, SJ'-diethoxy ^ '- diaminodiphenylsulfone, 3,3'-dichloro-4,4'-diaminodiphenyl sulfone.

SJ'-Diearboxy ^ 'diaminodiphenylsulfone, 3.3'-DihydiOxy-4.4'-diaminodiphenyl sulfone, SJ'-Disulfo ^ '- diaminodiphenylsulfone.

3,3'-diethyl-4,4'-diaminodipheny! Propane (2,2), 3,3'-dimethoxy-4,4'-diaminodiphenylpropane- (2,2), 3 T-dibromo-4,4'-diaminodiphenylpropane- (2,2), 3,3'-dichloro-4,4'-diaminodiphenylpropane- (2,2), 3.3'-dicarboxy-4,4'-diaminodiphenylpropane- (2,2), 3,3'-dihydroxy-4,4'-diaminodiphenylpropane- (2,2), 3,3'-DisuIfo-4.4'-diaminodiphenylpropane- (2,2), S ^ '- dimethyl ^ / T-diaminobenzophenone, S ^ '- Dimethoxy ^ / T-diaminobenzophenone,

SJ'-dichloro ^. ^ '- diaminobenzophenone, 3,3'-dibromo-4,4'-diaminobenzophenone.

SJ'-Dicarboxy ^ '- diaminobenzophenone, S.S'-dihydroxy ^ / l'-diaminobenzophenone, S.S'-DisuIfo ^^ '- diaminobenzophenon.

* »-Wr%" .. "- J * I-. _ I -. * U, * j, ~ j "L> l € lll III IUUI LHIWlYllllf-tllCltl.

3,3'-diaminodiphenyl sulfide,

3,3'-diaminodiphenyl sulfone.

3,3'-Diaminodiphenylpropane- (2.2).

S.S'-diaminobenzophenone, 3,3'-diaminotoluene, 2,6-diaminotoluene and

l-isopropyl-2,4-phenylenediamine. So that one can use linear aromatic polyimides with both very good solubility as well as having a good flexibility, the respective proportions of the components with the groups R and R 'in the above formula can be adjusted accordingly.

For the preparation of solutions of linear aromatic polyimides with a viscosity between and 100 poise at room temperature in a phenolic solvent with a resin content of 20%, which are suitable for lacquer coatings of so-called magnetic conductors, it is advisable that at least 55 Mol% of the tetracarboxylic acid used as benzophenone tetracarboxylic acid are present.

If this acid is present in a proportion of 55 to 65% and the remainder as pyromellitic acid, one obtains Polyimides with very high flexibility and softening when heated. In this case, it's for one high solubility expedient that at least 50% of the radicals of the diamine among the three general mentioned Formulas are selected.

Especially in the case when at least 50% of the SO,

are selected, maximum solubility is obtained. An inexpensive non-solvent such as toluene or xylene can be used as a diluent up to an upper limit of about 30%. A very dense coating layer can thus be produced from the resin obtained.
In cases where the diamine residues correspond to the formulas

HOOC

COOH

HO

OH

can correspond to the functional groups, such as COOH or OH, within the molecules Crosslinking elements such as diisocyanates are connected to one another, so that one has a crosslinked structure receives.

isolate according to the invention by adding a large amount of a nonsolvent to the resin solution, but you can also use the resin solution directly as a paint job, if you wish, by using a Modifier admits.

Examples of useful modifiers are diisocyanates, stabilized isocyanates and soluble polyester resins.

If necessary, an isolated polyimide can be dissolved in a solvent and used as a lacquer application will; it can also be used directly as a stabilizer for rubber, synthetic resins or the like, as well as Filler for ceramics and as resin raw material for compression molding technology.

The advantages achieved by the invention can be summarized as follows:

1) The linear aromatic polyimides obtained according to the invention are in a phenolic solvent soluble and do not need to be cooled in order to be used as a lacquer guarantee. In contrast to this, a well-known so-called polyimide varnish is a solution of a polyamide acid in a solvent where a gradual conversion to an insoluble polyimide occurs, if they are not kept in a refrigerated state

.: ..-: ji ^ "i. ^ n": .1- ..

y MIIIUItICI ^ C. LICI UCI

11 * "ll .." "

I 1 (.13ILIIUIIg

/1.3H-III IUI

Fr.

IU

Visc. the solution

Internal viscosity =

Visc. of the solver

ίο

2) A paint using one according to the invention obtained polyimide enables a clean coating layer to be formed without defects. If in In contrast to this, known polyamide lacquers are baked on, foams or bubbles appear of the water released from the polyamic acid, which affects the paint coating.

3) According to the invention, a complete elimination of water of the tetracurboxylic acid dianhydride is prior to the start the reaction is not necessary.

4) According to the process according to the invention, the reaction can be controlled in a comparatively simple manner as a polymer with a high degree of polymerization regardless of the order or the technique of adding the starting materials.

5) The invention enables the production of inexpensive

: j: 1 11lluu F Al

p-cresol
m-Crcsol
o-cresol
phenol

Weight%

40.0 53.7

2.5

3.8

Infrared analysis is done using KBr tablets. The absorption close to the 3400 cm- 'wavenumber in the infrared spectrum of FIG. 1 comes from the moisture content of the KBr.

Example 2

A similar procedure as in Example I is applied to the following starting materials and solvents used for the production of linear aromatic polyimides.

Workers only have a low risk of poisoning because the polyimides according to the invention are essentially are fully soluble in low-cost, non-toxic phenolic solvents.

25th

30th

The invention is illustrated in the following examples using preferred embodiments, the respective measured values being related to comparative examples. In Figs. 1 to 9 are each given infrared spectra of various embodiments of the invention.

example 1

A three-lug flask, the one with a thermometer, a stirrer, and a condenser is equipped with 32.2 g (0.1 mol)

S ^ '^ / l'-Benzophenonetetracarboxylic acid dianhydride, J5 22.8 g (0.1 mol) of 3,3'-dimethyl-4,4'-diaminodiphenylmelhane and 145 g of m-cresol were charged. The filling will then heated from room temperature to 60 ° C. with stirring, with progressive water formation occurs in the reaction mixture and the solution increases

Heating and stirring are continued for about 1 hour. After the water is distilled, the reaction begins interrupted (distilled amount 3.5 g). Acetone is gradually added to the resin solution obtained so that the Resin content fails. The resin precipitate is then washed out and in vacuo at room temperature dried. A polyimide resin of light yellow color is thus obtained in an amount of 48.8 g (95% Yield).

This resin does not melt up to 300 ° C. The intrinsic viscosity in m-Cresoi with a concentration of 0.5% is 0.72. The infrared spectrum of this resin is given in Fig. 1; a noticeable absorption occurs in the vicinity of the wave numbers 1780 cm- ¹ , 3730 cm- 'and 730 cm-', where the characteristic absorption bands of imides are located.

The intrinsic viscosity is calculated using the following equation:

3,3 ', 4,4'-benzophenone tetracarboxylic acid
3,3'-dichloro-4,4'-diaminodiphynyl methane

Commercially available xylenol

m-, p-cresol

2,4-2,5-xylenol

p-ethylphenol, 3,5-xylenol

rest

Reaction conditions
Amount of distilled
Water

35.8 g (0.1 mol)

26.9 g (0.1 mole) 150 g

27.9% 33.1% 31.6% 7.3% 170 ° C, 2 h

7.0 g.

The yield and characteristic of the obtained linear aromatic polyimide are as follows

yield
colour

Melting point
Infrared analysis

solution

95.5% light yellow about 300 ^° C. (spectrum according to FIG. 2) clear

Example 3

A similar procedure to Example 1 is followed the following raw materials and solvents to produce a linear aromatic polyimide applied.

3,3 ', 4,4'-benzophenone tetra-

carboxylic acid dianhydrides

3,3'-diaminodiphenyl sulfone

m-cresol

Reaction conditions

Amount of distilled

Water

32.2 g (0.1 mole) 24.8 g (0.1 mole) 150 g 160 ° C, 4h

3.4 g.

60

with C as the polymer concentration in g / 100 ml of the solution; the viscosity of the solution is the measured value of a 0.5% solution in m-cresol at 30 ⁰ C, the m-cresol used has the following composition:

The yield and characteristics of the obtained linear aromatic polyimide are as follows

Yield 95.5%

Colour: light yellow

Melting point over 300 ° C

Infrared analysis (spectrum according to

Fig. 3) Solution clear

Examples 4,5 and 6

In each case according to a corresponding procedure as in Example 1, the starting materials Solvents and reaction conditions of the following Table 1 prepared linear aromatic polyimides The respective yields and parameters of the polyimide resins obtained are also shown in Table 1 specified.

Tabel

Example 4

Raw material

3,3 ', 4,4' - 'benzophenone tetracarboxylic acid 3,3'-dimethoxy-4,4'-diaminodiphenylpropane- (2,2) 3,3'-dicarboxy-4,4'-diaminodiphenylmethane 3,3'-dihydro-4,4'-diaminodiphenyl ether 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide 3,3'-disulfo-4,4'-diaminodiphenylmethane

solvent
Commercially available xylenol

Reaction conditions
Temperature ('C)
Response time (h)

Parameters for the reaction product yield (%)
Melting point ( ⁰ C)
Internal viscosity
colour
Infrared analysis

Amount of distilled water

0.1 mole
0.1 mole

0.1 mole
0.1 mole

150 g

150 g

0.1 mole

0.1 mole

150 g

160 150 170 3 3 I. 95 96 95 L.-300 over 300 over 300 0.80 0.82 0.75 light yellow light yellow light yellow spectrum according to Fig. 4 6.9 g

Example 7

A similar procedure as explained in Example 1 is used for the following starting materials and Solvent to prepare a linear aromatic polyimide solution.

3,3 ', 4,4'-benzophenone tetra-

carboxylic acid dianhydride

3,3'-dimethyl-4,4'-diamino

diphenylmethane

4,4'-diaminodiphenyl ether

commercial xylenol

Reaction conditions

322 g (l mol)

137 g (0.6) mol) 80 g (0.4 mol) 1500 g 170 ⁰ C, 2 h

45

The polyimide solution thus obtained, the reaction solvent and a small amount of petroleum ether was added in order to obtain an enamel paint with 20% resin content This lacquer is applied directly to an annealed copper wire of 1.0 mm diameter and at a temperature of 400 ⁰ C at a flow rate of Baked at 8 m / min to obtain a magnetic conductor with a coating layer 0.047 mm thick. The characteristics of this magnetic conductor are as follows

Bubbles (number per 5 m)
Flexibility (smallest
Bending diameter)
usable diameter
Abrasion resistance,
repeated scraping
(700 g load)

Ix

60 repetitions

60

65 push-through temperature
(punctiform

crossing 700 g load) over 300 ° C Thermal shock (300 ° C, 1 h) 1 χ radius Well Breakdown voltage Normal state 16.8 kV after 24 hours Immersion in water 16.5 kV after heating, 200 ° C, 2h 16.5 kV CHC1F ₂ resistance Well

The flexibility is measured in such a way that a coated wire tightly around every 10 turns a series of cylindrical cores is wound, which have a diameter that is an integer Multiples of the wire diameter is equal. One examines the appearance of the coating with the Eye. The minimum diameter of the winding core at which there are no cracks is considered to be the smallest Bending diameter given in multiples of the wire diameter. The parameter »thermal shock« is measured by the fact that the coated wire is also fixed in 10 turns on a series of cylindrical Cores is wound by a thermostat over a certain period of time on a predetermined Temperature are maintained. The appearance of the coating is examined with the eye. Of the The smallest diameter of the winding core at which no cracks occur is used as a measure of the thermal shock taken.

Examples 8,9,10,11 and i2

Following a procedure similar to that in

Example I are explained, each using the starting materials according to Table 2 polyimide solutions prepared. The pofyimids are made from a part of this

Solutions separated and analyzed by infrared. In all cases, noticeable absorptions are observed near 1780 cm- ', 1730 cm-' and 730 cm- ', i.e. at the characteristic absorption bands of Imides.

Table 2

Raw material

example

10

12th

S ^ '- ^' - Benzophenone tetracarboxylic acid dianhydride 3,3'-diethyl-4,4'-diaminodiphenyl sulfone 3,3'-dimethoxy-4,4'-diaminodiphenyl ether 3,3'-dicarboxy-4,4'-diaminodiphenyl sulfide 3,3'-dihydroxy-4,4'-diaminodiphenylpropane (2.2) 3,3'-dianinodiphenylpropane (2.2) 3,3'-diaminodiphenyimethane

4,4'-diaminodiphenylmethane

4,4'-diaminodiphenyl ether

Benzidine

1,5-diaminonaphthalene

Mole 1 mole 1 mole 1 mole 1 mole

0.7 moles

0.6 MoI

0.7 mole 0.5 mole
0.8 moles

0.2 moles

0.2 moles
0.3 mol

0.4 mole 0.1 mole

0.2 mol

0.1 mol

These solutions are then adjusted to a resin content of 20% and used directly as a coating layer on an annealed copper wire of 1.0 mm Applied diameter and baked in a corresponding way JO as in Example 7. You get so Magnetic conductor with a 0.047 mm thick coating layer. The characteristics of the magnetic conductors are given in Table 3.

Table 3

test

example

10

12th

Bubbles (number per 5 m)

Flexibility (bending with your own diameter) (good, bad)

Abrasion resistance, repeated scratches, 700g load (repetitions) Push-through temperature (punctiform cutting 700 g load) (C)

0 0 0 0 0 Well Well Well Well Well

144

> 300 156

> 500

138

> 300

160

> 300

168

> 300

Thermal shock (300 C, 2 h) 1 x through 1 x through 1 x through 1 x through 1 x through knife good knife good knife good knife good knife good Breakdown voltage (kV) Normal state 16.7 16.5 16.9 16.7 16.4 after 24 hours of immersion in water 16.4 16.3 16.7 16.7 16.2 after heating, 200 C. 2 h 16.5 16.3 16.5 16.5 16.3 CIICH resistance Well Well Well Well Well

Examples 13, 14, 15, 16 and 17

The procedure of Example 1 is followed using that given in Table 4 Starting materials carried out for the purpose of producing appropriate polyimide solutions. After setting on With an ileal fraction of 20%, these solutions are immediately annealed as a coating layer on a Copper wire 1.0 mm in diameter is applied and then applied in a manner corresponding to that of Example 7 burned in. This gives magnetic conductors with a 0.047 to 0.048 mm thick coating layer. the Characteristics of these magnets are shown in the following Table 5 given.

19 62 588 15th Table 4 16 example 0.8 moles 0.7 moles 0.7 MoI 0.2 moles 0.3 mol 0.3 mole I.
I.
ί Breakdown voltage (kV) ϊ ■ "
S. Raw material 13 14 15 0.81 0.91 0.95 i Normal condition 16.5 Through- 1 x through- § 16.3 I. 0.7 mole 0.8 mole 0.7 mole 3.4 g after 24 hours of immersion in water 16.1 good knife good knife good knife good knife good | 16.0 < 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 0.3 mole 0.3 mole [ after heating at 200 ° C., 2 h 16.0 16.0 Pyromellitic dianhydride 0.2 moles 16 17 I.
Ϊ. CHCIf-y resistance good 16.4 16.7 16.5 Well ; 3,3 ', 4,4'-diphenyl tetracarboxylic acid 14 15 16 0.7 moles 0.8 moles f Infraro'iaralysis 16.2 16.4 16.4 2,2,6,7-naphthalene tetracarboxylic acid dianhydride 0 0 0 The polyimides are made from parts of the 16.0 16.5 16.1 inear aromatic 2,2-bis (3,4-dicarboxyphenyl) propane well well well I.
r, polyimide solutions obtained in the manner described well well well Bis (3,4-dicarboxyphenyl) ether 0.1 mol I separated and the parameters of the separated Spectrum according to FIG. 5 S ^ '- Dicarboxy ^^' - diaminodiphenylmethane 99 87 89 0.2 moles of I. Measured polyimides. All resins are light yellow in color ΐ5 solvent to produce a 3,3'-DiaminodiphenyIsulfide 0.2 moles of I. ί and a melting point above 300 ⁰ C. The infrared Polyimide running. 322 g (IMoI) 2,4-diaminotoluene 0.7 MoI \ Spectra of each polyimide show a noticeable one 124 g (0.5 mol),. 1-isopropyl-2,4-m-phenylenediamine 0.1 mol \ Absorption near 1780 cm- ¹ , 1730 cm "- ¹ and 3.3 ', 4,4'-benzophenone tetra- 100 g (0.5 mol) I. p-phenylenediamine 730 cm- ', i.e. the characteristic absorption carboxylic acid diaihydride 1500 g 1 4,4'-DiaminodiphenyIsuirone 0.7 moles I. bound by imides, the intrinsic viscosity of each bo 3,3'-diamineQdiphenylsulfQn 160 ° C, lh I 3,3'-dimethoxybenzidine 0.1 mol I these resins are shown in Table 4. 4,4'-diaminodiphenyl ether i 4,4'-diaminodiphenylpropane- (2.2) 0.2 moles of I. Example 18 iTi-Cresol 33 g. I. Internal viscosity 0.2 MoI j The procedure of Example 1 is shown under Reaction conditions The yield and the characteristics of the linear | Amount of distilled water ι Use of the following raw materials and solvents Amount of distilled aromatic polyimide are as follows. i Table 5 1.01 1.10 ^l 65 water Exam example i. 13th f Bubbles (number per 5 m) 0 1 Flexibility (turning with your own good ¹⁷ I. Diameter) (good, bad) ο i Abrasion resistance, repeated scratching 82 good I. 700 g load (repetitions) I. Penetration temperature (punctiform > 300 102 I. Crossing 700 g load) (C) 1 > 300> 300> 300> 300 I. Thermal shock (300 C, 2 h) Ix through- 1 x through- 1 x through- 1 x knife

I.
I 19 62 588 18th (Repetitions) 120 0.038 moles 0.055 moles 0.045 moles 0.045 mol 0.055 moles aromatic polyimides 0.1 I 17 Push-through temperature ι the same table 6 170 C, lh I yield 94.7% (punctiform diam 95.2 I solution light yellow, clear crossing 700 g load) Over 300 ° C 150 150 0.75 4 infrared spectrum (Fig. 6) Thermal shock (300 ⁰ C χ 2 h) I χ diameter Well 21 After the reaction has ended, 2 g of 5 Breakdown voltage 0.08 mole I added tetrabutyl titanate at room temperature, and Normal state 16.5 kV | j the mixture obtained is stirred. This paint after 24 hours 24 I is used as a top coat directly on one Immersion in water 16, ok 0.02 moles 0.07 moles jfi annealed copper wire with a radius of 1.0 mm after heating to 200 ⁰ C, I brought and at a stoving temperature of 350 ⁰ C io 2h 16.4 kV 0.03 moles I and a baking speed of 8 m / min.
I am on fire. This gives you a magnetic conductor with a CHCIF ₂ -resistant code Well I 0.045 mm thick top coat. The parameters 0.03 mol t of this magnetic conductor are as follows. Examples 19, 20, 21 22.23 and 24 S ^l5
ϊ Bubbles (number per 5 m) none The procedure of Example 1 is for the I flexibility (minimal Starting materials and solvents in Table 6 '■' bending diameter) 1 χ diameter executed so as to be linear 0.07 moles I Abrasion resistance receives. Their parameters are ir j (repeated scraping} 20 specified. 150 ["(700 g load) Lead naphthanate y-picoline ! Table 6 example 0.05 Raw material 19 20 170 C, 2 hours 160 C, 2 hours 0.07 mole 0.62 mole 96.0 96.2 ι 3,3 ', 4,4'-Benzophepontetracarbonsäure 0.03 moles 0.92 0.72 Pyromellitic acid Fig. 7 I 3,3 ', 4,4'-diphenyl tetracarboxylic acid 5.9 g j 2,3,6,7-naphthalene tetracarboxylic acid j 2,2-bis (3,4-dicarboxyphenyl) propane example j 3,3'-diaminodiphenyl sulfone 22 23 j 3,3'-diaminodiphenylmethane 0.09 mole 0.08 mole '3,3'-Diaminodiphenyl sulfide 2,4-diaminotoluoI 0.01 mole 4,4'-diaminodiphenylmethane ■ benzidine I 1,5-diaminonaphthalene ; 3,3'-dimethyl-4,4'-diaminodiphenylmethane \ Commercial xylenol (g) S reaction catalyst and amount added \ (% of the color) Reaction conditions (temperature, time) Yield (%) Logarithmic intrinsic viscosity ! Infrared spectrum Amount of distilled water I Table 6 (continued) I starting material I.
ί \ 3,3'-4,4'-Benzoephertintet-facarboxylic acid I pyromellitic acid 1 3 <3 ', 4,4'-DiphehylletfacarbönsäUfe

19th

continuation

Starting material "

example
22nd

24

2,3,6,7-naphthalene tetracarboxylic acid 2,2-bis (3,4-dic ^l' iboxyphenyl) propane

3,3'-diaminodiphenyl sulfone 3,3'-diaminodiphenyl imethane 3,3'-diaminodiphenyl sulfide 2,4-diaminotoluene 4,4'-diaminodiphenylmethitol benzidine

1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane Commercially available xylenol (g) reaction catalyst and amount added (% of the color)

Reaction conditions (temperature, time) yield (%)

Logarithmic intrinsic viscosity infrared spectrum

Amount of distilled water 0.01 mole

0.01 mol

0.045 moles 0.02 moles 0.035 mol 0.055 mol 0.02 moles 0.065 moles 150 150 180 C, 2 h 150 190 C. 1 h 93.8 180 C, 2 h 94.4 0.710 94.0 0.70 0.70

example

The procedure of the example is carried out using the following starting materials and solvents designed to produce a linear aromatic polyimide using a small amount of petroleum ether Preparation of an enamel varnish with 20% resin is added.

3,3 ', 4,4'-benzophenone telra-

carboxylic acid dianhydride 0.55 mol

Pyromellitic acid dianhydride 0.45 mol

3,3'-diaminodiphenyl isulfone 0.40 mol

4,4'-D ⁱ aminod ^: ₁ phenyl ether 0.60 mol

Commercially available xylenol
Tetrabutyl titanate

Reaction conditions
Amount of distilled
Water

1500 g
0.44 g (0.1%
Resin content)
170C. 1 h

34.0 g.

The enamel paint obtained in this way is applied as an overlay on an annealed copper wire 1.0 mm in diameter applied and in the same way as explained in Example 7, baked, so that one Magnetic conductor with the following parameters. The values for an example 25a are also given.

Blisters (number per 5 m) Flexibility (minimum bending diameter) Abrasion resistance, repeated scraping, repetitions (700 g load) Push-through temperature (punctiform crossing 700 g load)
Thermal shock (300 ° C, 2 h)

Breakdown voltage (kV) Normal state after being immersed in water for 24 hours after heating to 200 ° C, 2 h

Aging test (25O ⁰ C, bent 6 h after heating)

Overload test (time until a 20 mA loss ^ Current flows when a 40 A current is twisted through a Pair of conductors flows)

Example 25 Example 25 a 0 0 1 x diameter 1 x diameter 76 74 300 C 300 C 1 x diameter good 1 x diameter good 16.7 16.8 16.5 16.5 16.4 16.4 1 X diameter good 3 X diameter good 30-50 min 10-15 min

for the above example 25a a polyimide in in the same way as in Example 25 with equimolar amounts of JJ '/ W-Benzophynontetracarbonsäuredianhydrid and 3,3'-diaminodiphenylsulfon produced. This polyimide is placed on an electrical conductor The same conditions as in Example 25 are applied and baked, so that a magnetic conductor is obtained. The intrinsic viscosity of the polyimide of this Example 25

is 0.78. the infrared spectrum is in Fig. 8 specified.

Examples 26, 27, 28 and 29

In a manner similar to that explained in Example I, is obtained linear aromatic polyimides using the starting materials and solvents according to Table 7. The yields and internal viscosities of these polyimides are also shown in Table 7.

Table 7

Starting material (mol)

example

27

29

0.30

20/80

0.45

0.45

0.55 0.45

0.55

0.58

0.42

0.30
0.70

0.5

0.30 0.40

0.58

SJVl ^ '- Benzophenone tetracarboxylic dianhydride

3,3 ', 4,4'-Benzophenone tetracarboxylic acid methyl ester

Bis (3,4-dicarboxydiphenyl) sulfone bis (3,4-dicarboxyphenyl) ether

3,3'-Diaminodiphenylpropane- (2,2) 3,3'-Diaminodiphenylsulfone

2,6-diaminotoluene

2,4-diaminotoluene

4,4'-Diaminodiphenylpropane- (2j2) 4,4'-Diaminodiphenylmethane

4,4'-diaminodiphenyl ether

4,4'-diaminodiphenyl sulfone

m-phenylenediamine

Commercially available xylenol (g)

Reaction catalyst and amount added (% of the resin content)

Reaction conditions (temperature, time) yield (%)
Internal viscosity

Note: The 3,3 ', 4,4'-Benzophenontetracarbonsäuremethylester has an acid number of 287.4 (corresponding to dimethyl ester).

Examples 30, 31, 32 and 33

Using the starting materials according to Table 8, a method similar to that in the example is obtained 1 polyimide solutions. These polyimide solutions are used in accordance with Example 7 with enamel paints Prepared with a 20% resin content.

1500 0.25 0.32 Lead- 0.1 naphthalene 0.0 0.25 1500 170 ⁰ C, 1 h 1500 1500 95.0 Lead- 0.79 naphthäriatO.l 190 ⁰ C, 2 h 170 ° C, 1 h 170 ⁰ C, 1 h 93.0 95.5 96.0 0.81 0.91 1.02

Table 8

Starting material (MbI)

example
30th

32

3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 3,3 ', 4,4'-Benzophenonetetracarboxylic acid ethyl ester 3,3'-Dimethyl-4,4'-diaminodiphenylmethane 3,3'-dimethoxy-4,4'-diaminodiphenyl ether 3,3'-dicarboxy-4,4'-diaminodiphenyl sulfide 3,3'-diaminodiphenyl sulfone

1
0.3

1
0.7

0.1

0.4

continuation

23

Starting material (mol) example
30th

32

33

30/70

p-xylylinediamine, m-xylylinediamine 4,4'-Didminodiphertylmethane Benzidine

4,4'-Diaminodiphenyliither

Amount of distilled water

0.1
0.1

33, Sg

0.3 0.3

0.5

The enamels obtained are applied as a coating and baked on soft copper wires with a diameter of 1.0 mm and an internal viscosity value above 300 ° C. So you get
Magnetic liter with 0.047 to 0.048 thick coating layer,
whose parameters are given in Table 9.

between 0.81 and 1.20 (0.5% concentration in Dimethyl acetate at 30 "C).

Table 9

test

example 31 32 33 30th 0 0 0 0 Well Well Well Well

Blisters (number per 5 m) Flexibility (bending with its own diameter) (good, bad) resistance to scratching, repeated scratching 700 g load (repetitions) push-through temperature (punctiform crossing 700 g load) (T) thermal shock 300 C, 2 h

Breakdown voltage (kV) normal state after immersion in water for 24 ^{hours after heating to 200 °} C. for 2 hours

CHCIFz activity infrared analysis

69

> 300 81

> 300

69

> 300

84

> 300

1 X diameter- 1 X diameter- 1 X diameter- 1 X diameter good knife good knife good knife good

16.4 16.4 spectrum 16.4 16.5 16.2 16.6 16.2 16.3 16.2 16.5 16.3 16.3 Well Well Well Well according to FIG. 9

Examples 34, 35, 36, 37, 38 and

With the starting materials and solvents according to Table 10 one obtains in a corresponding procedure, as in Example 1, linear aromatic polyimides. The measured values are entered in the same table 10.

Table 10

Raw material

Example 34

36

3,3 ', 4,4'-benzophenone tetracarboxylic acid 3,3', 4,4'-benzophenone tetracarboric acid Pyromellitic acid 3,3 ', 4,4'-diphenyltetracarboxylic acid 2,3,6,7-naphthalenetetracarboxylic acid 2,2'-bis- (3,4-dicarboxyphenyl) propane- (2,2) 2,4-diaminoanisole 2,4-diaminomonochlorobenzene 2,4-diaminobenzoic acid

0.1 mole 0.07 mole

0.03 moles

0.055 mole 0.04 mole

0.08 mole

0.02 moles

0.05 moles

25th

continuation

Raw material

example
.14

35

36

2,4-diaminophenol 2,4-diaminobenzenesulfonic acid 4,4'-biaminodiphenyl ether 4,4'-diaminodiphenylmethari benzidine

4,4'-diaminodiphenylpropane 1,5-diaminonaphthalene Commercially available xylenol (g) m-cresol (g)

Reaction catalyst and amount added (% of the resin content)

Reaction conditions (temperature, time) yield (%)
Internal viscosity

0.045 moles

0.06 moles

0.05 moles

150 150 150 150 Tetrabutyltitahat Bieinaphthenate 0.05 0.05 160 "C, 1 h 160 ⁰ C, 1 h 170 ° C, 1 h 94.8 95.0 95.2 0.90 0.95 1.15

Table 10 (continued)

Raw material

example
37

3,3 ', 4,4'-benzophenone tetracarboxylic acid 3,3', 4,4'-benzophenone tetracarboxylic acid Pyromellitic acid

3,3 ', 4,4'-diphenyl tetracarboxylic acid 2,3,6,7-naphthalene tetracarboxylic acid 2,2'-bis (3,4-dicarboxyphenyl) propane (2,2) 2,4-diaminoanisole 2,4-diaminomonochlorobenzene 2,4-diaminobenzoic acid 2,4-diaminophenol 2,4-diaminobenzenesulfonic acid 4,4'-diaminodiphenyl ether 4,4'-diaminodiphenylmethane benzidine

4,4'-diaminodiphenylpropane 1,5-diaminonaphthalene Commercially available xylenol (g) m-cresol (g)

Reaction catalyst and amount added (% of the resin content)

Reaction conditions (temperature, time) yield (%)
Internal viscosity

example

Proceeding from the following starting materials and a solvent, the procedure of Example 1 prepared a linear aromatic polyimide.

0.06 moles
0.04 moles

0.03 moles

0.07 moles

0.03 moles

0.45 moles

39

0.1 mole

f! ', 02 mol

0.02 moles

0.07 moles 0.055 moles' y-picoline 0.1 0.06 Mole 150 180'C, lh 170'C, 2h 93.7 96.1 150 0.81 0.73 3,3 ', 4,4'-benzophenone tetra-
carboxylic acid dianhydride
33'-diaminobenzophenone
Commercially available xylenol
Reaction conditions 180 ' C, 2 h 94.0 0.86 32.2 g (0.1
21.2 g (0.1
150 g
17 ° C, 1 h Mole)
Mole)

27

Bulge and characteristics of this linear aromatic Polyimides are as follows

yield

Amount of distilled

95% water

Solution light yellow clear
Melting point above 300 ^° C
Internal viscosity

3.5 g

0.86

Examples 41, 42, 43, 44 and 45

With the starting materials and solvents and parameters of the respective polyimides are in Table 11 shows linear aromatic polyimides according to Table 11, using the procedure of Example 1. The yield io

Table 11

Raw material

Example 41 42

43

45

.liVM'-Benzophenonetetracarboxylic acid dianhydride

S ^ '^' - dimethyl betizophenone tetracarboxylate

Pyromellitic acid

Bis (3,3-dicarboxyphenyl) ether

3,3'-dimethyl-4,4'-diaminobenzophenone 3,3'-dibromo-4,4'-diaminobenzophenone 3,3'-Dioxy-4,4'-diaminobenzophenone 3,3'-Dimethoxy-4,4'-diaminobenzophenone 3,3'-Diaminobenzophenone 4,4'-Diaminodiphenylmethane 4,4'-Diaminodiphenyl ether 4,4'-Diaminodiphenylpropane 4 4'-diaminodiphenyl sulfone

OJ Mol Oi Mol 0 _? 07 moles 0.08 MnI

0.02 mole 0.07 mole

0.03 moles

0; 1 mole 0.1 mole

0.05 moles

0.05 moles

0.06 moles

0.04 moles

0.03 moles

0.05

p-phenylenediamine 150 150 150 150 0.03 moles Benzidine 160 ° C, 2 h 160 ⁰ C, 2 h 170 ¹ C, lh 170 ⁰ C, 1 h 0.02 moles Commercially available xylenol (g) 94.5 95.0 96.0 94.8 150 Reaction conditions (temperature, time) 0.78 0.86 0.75 0.91 170'C 1 Yield (%) Comparative example 94.5 Internal viscosity 0.89

The following starting materials and solvents are at 125 ° C for a period of 3 hours brought into action on each other.

3,3 ', 4,4'-Benzophenonetetracarboxylic acid dianhydride 4,4'-Diaminodiphenylether m-cresol

16.1 g (0.05 mol) 12.4 g (0.05IvIoI) 180 g A clear lacquer is obtained, which is applied to a copper plate and baked. The coating layer obtained with a thickness of 20 μ is bent over at an angle of 180 °, with cracks being formed. When map. also this paint takes at 17O ⁰ C for 3 hours for reaction, the resin fraction is precipitated.

For this purpose 3 sheets of drawings

Claims (1)

Claim: Process for the preparation of linear aromatic compounds soluble in phenolic solvents Polyimides by reacting equimolar amounts of at least one aromatic tetracarboxylic acid, their anhydride or their lower alkyl ester and at least one aromatic diamine in one Phenol-based solvent and heating the resulting solution to a temperature above the boiling point of water, thereby characterized in that at least 30% of the tetracarboxylic acid has a structure of the formula